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WO1996041858A1 - Diluted aqueous tenside solution with increased viscosity - Google Patents

Diluted aqueous tenside solution with increased viscosity Download PDF

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Publication number
WO1996041858A1
WO1996041858A1 PCT/EP1996/002387 EP9602387W WO9641858A1 WO 1996041858 A1 WO1996041858 A1 WO 1996041858A1 EP 9602387 W EP9602387 W EP 9602387W WO 9641858 A1 WO9641858 A1 WO 9641858A1
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WIPO (PCT)
Prior art keywords
carbon atoms
alkyl
surfactant mixtures
mixtures according
contain
Prior art date
Application number
PCT/EP1996/002387
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German (de)
French (fr)
Inventor
Thomas Förster
Jörg KAHRE
Markus Sumser
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1996041858A1 publication Critical patent/WO1996041858A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/32—Protein hydrolysates; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention relates to dilute aqueous surfactant solutions with increased viscosity, containing selected ternary surfactant mixtures based on alkyl and / or alkenyl ligoglycosides, betaines and selected other surfactants.
  • the complex object of the invention was therefore to provide aqueous surfactant mixtures based on alkyl and / or alkenyl oligoglucosides which, despite their high dilution, have a sufficiently high viscosity without the necessity of using organic thickeners.
  • the invention relates to dilute surfactant mixtures with increased viscosity, containing 30 to 70% by weight of alkyl and / or alkenyl oligoglycosides, based on the surfactant content a),
  • co-surfactants selected from the group consisting of fatty alcohol ether sulfates, monoglyceride (ether) sulfates, acylglutamates and protein hydrolyzates, with the proviso that the amounts add up to 100% by weight of active substance.
  • ternary mixtures of the type mentioned show viscoelastic behavior and a viscosity (shear rate 1 / s) in the range from 1,000 to 50,000 mPas even in dilute aqueous solution.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (I) R 1 O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/03977.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is also possible.
  • betaines and "real" amphoteric surfactants reference is made to the contribution by U.Ploog in Seifen- ⁇ le-Fette-Wwachs, 198, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (I)
  • R 2 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 3 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 4 for alkyl radicals with 1 to 4 carbon atoms
  • n for numbers from 1 to 6
  • X for is an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are are the carboxymethylation products of Hexylmethyl-amine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, Do- decyldimethylamine, Dodecylethylmethylamin, C dimethylamine 12/14 -Kokosalkyldimethylamin, myristyl, cetyldimethylamine, stearyldimethylamine methylamine, stearyl, Oleyldi-, C 16/18 -Talgalkyldimethylamin and their technical mixtures.
  • R 5 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m represents numbers from 1 to 3 and R 3 , R 4 , n and X have the meanings given above.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • R 6 is an alkyl radical having 5 to 21 carbon atoms
  • R 7 is a hydroxyl group
  • an OCOR 6 or NHCOR 6 radical and m is 2 or 3.
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • ether sulfates Fatty alcohol ether sulfates
  • CSA chlorosulfonic acid
  • ether sulfates which follow the formula (IV) are suitable
  • R 8 O- (CH 2 CH 2 O) m SO 3 Z (IV) in R 8 for a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, n for numbers from 1 to 10 and Z for a Alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, ela-alcohol alcohol, ela-alcohol alcohol, ela-alcohol alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution.
  • ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized.
  • suitable sulfating agents preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. WO 92/09 569, WO 92/09 570 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 42 04 700 (Henkel)].
  • R 9 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and Z stands for an alkali or alkaline earth metal.
  • Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
  • Monoglyceride sulfates of the formula (V) are preferably used in which R 9 CO represents a linear acyl radical having 8 to 18 carbon atoms.
  • R 10 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and Z represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammomum, alkanolammonium or glucammonium.
  • They are produced, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or chlorides. Sales products are available, for example, from Hoechst AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP.
  • An overview of the production and properties of the acylglutamates can be found by M.Takehara et al. in J. Am. Oil. Chem. Soc, 49, 143 (1972). Mixtures of alkyl glucosides and acyl glutamates are described in Japanese patent application JP-A Hl / 178 597 (Shiseido).
  • glutamic acid is one of the products that would be obtained by total hydrolysis of proteins.
  • the hydrolysis of proteins leads to mixtures of oligopeptides which still have an average of 5 to 20 amino acid units.
  • conventional protein fatty acid condensates represent acylation products of oligopeptides.
  • Acylglutamates differ from these substances in that they represent "monomers" to a certain extent.
  • acylglutamates which are suitable for the purposes of the invention are anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18 carbon atoms, such as C 12/14 - or C 12/18 - Coconut fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid.
  • anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18 carbon atoms, such as C 12/14 - or C 12/18 - Coconut fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid.
  • Sodium N-cocoyl and sodium N-stearoyl-L-glutamate are particularly preferred.
  • Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein and in particular wheat and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in the range of 600 have up to 4000, preferably 2000 to 3500.
  • protein hydrolyzates do not represent a surfactant in the classic sense due to the lack of a hydrophobic residue, they are widely used for the formulation of surface-active agents because of their dispersing properties. Overviews of the manufacture and use of Protein hydrolyzates are, for example, from G. Schuster and A. Domsch in Seifen ⁇ le Fette Wachsen, 108, 177 (1982) and Cosm.Toil, respectively. 99, 63 (1984), by HW Steisslinger in Parf.
  • liquid personal cleansing agents are also known which, in addition to alkyl glucosides and protein hydrolyzates, can also contain betaines in minor amounts.
  • the mixtures according to the invention are prepared, for example, by mixing the individual surfactants with heating.
  • low-viscosity binary premixes are produced, for example from 25 to 75% by weight of the amount of component a) to be used and 100% of the amount of component c) on the one hand and on the other hand from the remaining amount of component a) and 100% by weight of component b);
  • Components a) and b) are interchangeable in this example.
  • the surfactant mixtures according to the invention preferably contain components a), b) and c) in the weight ratios (30 to 50): (15 to 35): (15 to 35).
  • Diluted agents are to be understood as meaning those which have an active substance content (non-aqueous content) in the range from 5 to 20 and in particular 10 to 15% by weight.
  • the surfactant mixtures according to the invention are distinguished by a sufficiently high viscosity in the range from 1,000 to 50,000 mPas (shear rate 1 / s) and advantageous oscillating properties. They are suitable, for example, for cleaning hard surfaces and in particular as body and hair cleaning and care products, such as, for example, hair shampoos, hair lotions or bubble baths, and can be used in this connection as typical ingredients, emulsifiers, and over contain greasing agents, thickening agents, cation polymers, silicone compounds, biogenic agents, film formers, preservatives, colorants and fragrances.
  • Suitable emulsifiers are both known W / O and O / W emulsifiers such as, for example, hardened and ethoxylated castor oil, polyglycerol fatty acid esters or polyglycerol polyricinoleates or polyglycerol poly-12-hydroxystearates.
  • Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
  • Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as, for example, fatty alcohol distribution with fatty alcohols such as fatty alcohol or alkyl oligoglucosides and electrolytes such as table salt and ammonium chloride.
  • polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized Vmylpyrrolidon / vinylimidazole polymers such as, for example, Luviquat® (BASF AG, Ludwigshafen / FRG), condensation products of polyglycols and amines, such as, for example, collagen hydrolyzylated collagen polypolyphenolated collagen polypropylene (Lamequat®L, Grünau GmbH), polyethyleneimine, cationic silicone polymers such as Amidomethicone or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetrimamine (Cartaretine®, Sandoz / CH), polyaminopolyamides as described, for example, in FR-A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine and / or alkyl modified silicone compounds.
  • Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpy ⁇ Olidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
  • Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters.
  • the dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
  • the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.
  • aqueous surfactant mixtures with an active substance content of 12% by weight, optionally with the addition of 1 to 3% by weight of sodium chloride, based on the solids content of the mixtures, were investigated at 20 ° C. in a Rheometrics RFSII rotary rheometer.
  • the viscosity was determined at a shear rate of 1 or 30 s / m and in oscillation experiments, the modulus of elasticity G 'and the viscosity modulus G ".
  • APG coconut alkyl oligoglucoside (Plantaren® APG 1200)
  • FAES fatty alcohol ether sulfate (Texapon® NSO)
  • ACG acylglutamate (Hostapon® KCG)
  • WPHY wheat protein hydrolyzate (Gluadin® WK)
  • CMGS coconut monoglyceride sulfate sodium salt

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Abstract

The proposal is for diluted tenside mixtures with increased viscosity containing as tenside components, a) 30 to 70 wt. % alkyl and/or alkenyl oligoglycosides, b) 15 to 50 wt. % betaine tensides and c) 15 to 50 wt. % Co tensides selected from the group consisting of fatty alcohol ether sulphates, monoglyceride (ether) sulphates, acyl glutamates and protein hydrolysates, with the proviso that the quantities produce a total of 100 wt. % active substance.

Description

VERDÜNNTE WÄSSRIGE TENSIDLÖSUNG MIT ERHÖHTER VISKOSITÄT  DILUTED AQUEOUS SURFACTANT SOLUTION WITH INCREASED VISCOSITY
Gebiet der Erfindung Field of the Invention
Die Erfindung betrifft verdünnte wäßrige Tensidlösungen mit erhöhter Viskosität, enthaltend ausgewählte ternäre Tensidmischungen auf Basis von Alkyl- und/oder Alkenyl- ligoglykosiden, Betainen und ausgewählten weiteren Tensiden. The invention relates to dilute aqueous surfactant solutions with increased viscosity, containing selected ternary surfactant mixtures based on alkyl and / or alkenyl ligoglycosides, betaines and selected other surfactants.
Stand der Technik State of the art
Viele Anwendungen tensidischer Formulierungen im Bereich der Körperreinigung und der Reinigung harter Oberflächen setzen die Einstellung einer geeigneten Viskosität voraus. Gerade in verdünnten wäßrigen Systemen auf Basis von nichtionischen Tensiden vom Alkyl- glucosidtyp bereitet die Einstellung einer ausreichend hohen Viskosität, die eine einfache Dosierung einerseits und ein langsames Ablaufen an geneigten Flächen andererseits sicherstellt, Probleme. Many applications of surfactant formulations in the field of body cleaning and cleaning hard surfaces require the setting of a suitable viscosity. Particularly in dilute aqueous systems based on nonionic surfactants of the alkyl glucoside type, the setting of a sufficiently high viscosity, which ensures simple metering on the one hand and slow running on inclined surfaces on the other hand, creates problems.
Natürlich sind aus dem Stand der Technik eine Vielzahl von Verdickungsmitteln bekannt, zu denen neben Elektrolytsalzen und Fettsäurealkanolamiden auch ethoxylierte Fettalkohole [EP-A2 0 343 463 (Henkel)], Glucamide [DE-A1 37 11 776 (Hüls)], hochethoxylierte Glycerinfettsäureester [DE-A1 41 37 317 (Henkel)], Behenyltrimethylammoniumsalze und amphotere Tenside vom Sultaintyp zählen [Parf. Kosm. 76, 42 (1995)] In der Praxis erweisen sich aber gerade Alkylglucoside als besonders schwerverdickbar. Hinzu kommt, daß die Anwesenheit verschiedener Verdickungsmittel entweder aus ökotoxikologischen oder anwendungstechnischen Gründen im Rahmen einer kosmetischen Verwendung vielfach nicht erwünscht ist. Of course, a large number of thickeners are known from the prior art, to which, in addition to electrolyte salts and fatty acid alkanolamides, also ethoxylated fatty alcohols [EP-A2 0 343 463 (Henkel)], glucamides [DE-A1 37 11 776 (Hüls)], highly ethoxylated glycerol fatty acid esters [ DE-A1 41 37 317 (Henkel)], behenyltrimethylammonium salts and amphoteric surfactants of the sultain type include [Parf. Cosm. 76, 42 (1995)] In practice, however, alkyl glucosides prove to be particularly difficult to thicken. In addition, the presence of various thickeners either from ecotoxicological or application-technical reasons in the context of a cosmetic use is often not desired.
Die komplexe Aufgabe der Erfindung hat somit darin bestanden, wäßrige Tensid- gemische auf Basis von Alkyl- und/oder Alkenyloligoglucosiden zur Verfügung zu stellen, die trotz hoher Verdünnung eine ausreichend hohe Viskosität aufweisen, ohne daß hierzu die Mitverwendung von organischen Verdickungsmitteln zwingend erforderlich ist. The complex object of the invention was therefore to provide aqueous surfactant mixtures based on alkyl and / or alkenyl oligoglucosides which, despite their high dilution, have a sufficiently high viscosity without the necessity of using organic thickeners.
Beschreibung der Erfindung Description of the invention
Gegenstand der Erfindung sind verdünnte Tensidgemische mit erhöhter Vikosität, enthaltend bezogen auf den Tensidanteil a) 30 bis 70 Gew.-% Alkyl- und/oder Alkenyloligoglykoside, The invention relates to dilute surfactant mixtures with increased viscosity, containing 30 to 70% by weight of alkyl and / or alkenyl oligoglycosides, based on the surfactant content a),
b) 15 bis 50 Gew.-% Betaintenside und b) 15 to 50% by weight betaine surfactants and
c) 15 bis 50 Gew.-% Co-Tenside ausgewählt aus der Gruppe, die gebildet wird von Fettalkoholethersulfaten, Monoglycerid(ether)sulfaten, Acylglutamaten und Proteinhydrolysaten, mit der Maßgabe, daß sich die Mengenangaben zu 100 Gew.-% Aktivsubstanz ergänzen. c) 15 to 50% by weight of co-surfactants selected from the group consisting of fatty alcohol ether sulfates, monoglyceride (ether) sulfates, acylglutamates and protein hydrolyzates, with the proviso that the amounts add up to 100% by weight of active substance.
Überraschenderweise wurde gefunden, daß ternäre Mischungen der genannten Art auch in verdünnter wäßriger Lösung ein viskoelastisches Verhalten und eine Viskosität (Schergeschwindigkeit 1/s ) im Bereich von 1.000 bis 50.000 mPas zeigen. Surprisingly, it was found that ternary mixtures of the type mentioned show viscoelastic behavior and a viscosity (shear rate 1 / s) in the range from 1,000 to 50,000 mPas even in dilute aqueous solution.
Alkyl- und/oder Alkenyloligoglykoside Alkyl and / or alkenyl oligoglycosides
Alkyl- und Alkenyloligoglykoside stellen bekannte nichtionische Tenside dar, die der Formel (I) folgen, R1O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 KohlenstofFatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP-A1-0 301 298 und WO 90/03977 verwiesen. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl-und/ oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (I) R 1 O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1-0 301 298 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
Die Indexzahl p in der allgemeinen Formel (I) gibt den Oligomerisierungsgrad (DP-Grad), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylund/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. The index number p in the general formula (I) indicates the degree of oligomerization (DP degree), i.e. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and can in particular assume the values p = 1 to 6, the value p is for a specific alkyl oligoglycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
Der Alkyl- bzw. Alkenylrest R1 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capron- alkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). The alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C 8 -C 10 (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C 12 - Alcohol can be contaminated and alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3).
Der Alkyl- bzw. Alkenylrest R1 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3. The alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, Myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
Betaine Betaine
Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylierung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von ungesättigten Carbonsäuren wie beispielweise Acrylsäure möglich. Zur Nomenklatur und insbesondere zur Unterscheidung zwischen Betainen und "echten" Amphotensiden sei auf den Beitrag von U.Ploog in Seifen-Öle-Fette- Wachse, 198, 373 (1982) verwiesen. Weitere Übersichten zu diesem Thema finden sich beispielsweise von A.O'Lennick et al. in HAPPI, Nov. 70 (1986), S.Holzman et al. in Tens. Det. 23, 309 (1986), RBibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) und P.Ellis et al. in Euro Cosm. 1, 14 (1994). Aus der Deutschen Patentanmeldung DE-A1 42 34 487 (Henkel) sind zudem Handgeschirrspülmittel mit einem Gehalt an Alkylglucosiden, Betainen und Fettalkoholpolyglycolethern bekannt; hier werden die Glucoside jedoch nur als Co-Tensid eingesetzt. Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids such as acrylic acid is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U.Ploog in Seifen-Öle-Fette-Wwachs, 198, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Det. 23: 309 (1986), RBibo et al. in Soap Cosm. Chem. Spec. Apr. 46 (1990) and P.Ellis et al. in Euro Cosm. 1, 14 (1994). From the German patent application DE-A1 42 34 487 (Henkel), hand dishwashing detergents containing alkyl glucosides, betaines and fatty alcohol polyglycol ethers are also known; here the glucosides are only used as co-surfactants.
Beispiele für geeignete Betaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (I) folgen, Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (I)
Figure imgf000006_0001
in der R2 für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R3 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R4 für Alkylreste mit 1 bis 4 Kohlen Stoffatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht.
Figure imgf000006_0001
in which R 2 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 3 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 4 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for is an alkali and / or alkaline earth metal or ammonium.
Typische Beispiele sind sind die Carboxymethylierungsprodukte von Hexylmethyl-amin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Do- decyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyl- dimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldi- methylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische. Typical examples are are the carboxymethylation products of Hexylmethyl-amine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, Do- decyldimethylamine, Dodecylethylmethylamin, C dimethylamine 12/14 -Kokosalkyldimethylamin, myristyl, cetyldimethylamine, stearyldimethylamine methylamine, stearyl, Oleyldi-, C 16/18 -Talgalkyldimethylamin and their technical mixtures.
Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoamiπen in Betracht, die der Formel (II) folgen, Carboxyalkylation products of amidoamines which follow the formula (II) are also suitable,
Figure imgf000007_0001
in der R5CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R3, R4, n und X die oben angegebenen Bedeutungen haben.
Figure imgf000007_0001
in which R 5 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R 3 , R 4 , n and X have the meanings given above.
Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylamino- ethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethyl-ami- nopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat. Weiterhin kommen als geeignete Ausgangsstoffe für die im Sinne der Erfindung einzusetzenden Betaine auch Imidazoline in Betracht, die der Formel (III) folgen, Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate. Furthermore, suitable starting materials for the betaines to be used in the context of the invention are also imidazolines which follow the formula (III)
Figure imgf000008_0001
in der R6 für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R7 für eine Hydroxylgruppe, einen OCOR6- oder NHCOR6-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar.
Figure imgf000008_0001
in which R 6 is an alkyl radical having 5 to 21 carbon atoms, R 7 is a hydroxyl group, an OCOR 6 or NHCOR 6 radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines.
Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
Fettalkoholethersulfate Fatty alcohol ether sulfates
Fettalkoholethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkoholpolyglycolethern und nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht, die der Formel (IV) folgen, Fatty alcohol ether sulfates ("ether sulfates") are known anionic surfactants which are produced on an industrial scale by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention, ether sulfates which follow the formula (IV) are suitable
R8O-(CH2CH2O)mSO3Z (IV) in der R8 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 KohlenstofFatomen, n für Zahlen von 1 bis 10 und Z für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind die Sulfate von Anlagerungsprodukten von durchschnittlich 1 bis 10 und insbesondere 2 bis 5 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetyl-alkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, in Form ihrer Natrium- und/oder Magnesiumsalze. Die Ethersulfate können dabei sowohl eine konventionelle als auch eine eingeengte Homologenverteilung aufweisen. R 8 O- (CH 2 CH 2 O) m SO 3 Z (IV) in R 8 for a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, n for numbers from 1 to 10 and Z for a Alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, ela-alcohol alcohol, ela-alcohol alcohol, ela-alcohol alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts. The ether sulfates can have both a conventional and a narrow homolog distribution.
Besonders bevorzugt ist der Einsatz von Ethersulfaten auf Basis von Addukten von durchschnittlich 2 bis 3 Mol Ethylenoxid an technische C12/14- bzw. C12/18- Kokosfettalkoholfraktionen in Form ihrer Natrium- und/oder Magnesiumsalze. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
Monoglycerid(ether)sulfate Monoglyceride (ether) sulfates
Monoglyceridsulfate und Monoglyceridethersulfate stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Üblicherweise geht man zu ihrer Herstellung von Triglyceriden aus, die gegebenenfalls nach Ethoxylierung zu den Monoglyceriden umgeestert und nachfolgend sulfatiert und neutralisiert werden. Gleichfalls ist es möglich, die Partialglyceride mit geeigneten Sulfatierungsmitteln, vorzugsweise gasförmiges Schwefeltrioxid oder Chlorsulfonsäure umzusetzen [vgl. WO 92/09 569, WO 92/09 570 (Henkel)]. Die neutralisierten Stoffe können - falls gewünscht - einer Ultrafiltration unterworfen werden, um den Elektrolytgehalt auf ein gewünschtes Maß zu vermindern [DE-A1 42 04 700 (Henkel)]. Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. WO 92/09 569, WO 92/09 570 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE-A1 42 04 700 (Henkel)].
Übersichten zur Chemie der Monoglyceridsulfate sind beispielsweise von A.K.Biswas et al. in J. Am. Oil. Chem.Soc. 37, 171 (1960) und F.U.Ahmed J. Am. OH. Chem. Soc. 67, 8 (1990) erschienen. Mischungen von Monoglyceridsulfaten und Alkylglucosiden sind Gegenstand der Internationalen Patentanmeldung WO 95/06702 (Henkel). Die im Sinne der Erfindung einzusetzenden Monoglycerid(ether)suIfate folgen der Formel (V), Overviews of the chemistry of the monoglyceride sulfates are, for example, by AKBiswas et al. in J. Am. Oil. Chem.Soc. 37, 171 (1960) and FUAhmed J. Am. OH. Chem. Soc. 67, 8 (1990). Mixtures of monoglyceride sulfates and alkyl glucosides are the subject of international patent application WO 95/06702 (Henkel). The monoglyceride (ether) sulfates to be used for the purposes of the invention follow the formula (V)
Figure imgf000010_0001
Figure imgf000010_0001
in der R9CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und Z für ein Alkali- oder Erdalkalimetall steht. in which R 9 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and Z stands for an alkali or alkaline earth metal.
Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (V) eingesetzt, in der R9CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (V) are preferably used in which R 9 CO represents a linear acyl radical having 8 to 18 carbon atoms.
Acylglutamate Acylglutamates
Acylglutamate stellen bekannte anionische Tenside dar, die der Formel (VI) folgen, Acylglutamates are known anionic surfactants which follow the formula (VI)
Figure imgf000010_0002
in der R10CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 und/oder 1, 2 oder 3 Doppelbindungen und Z für Wasserstoff, ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammomum, Alkanolammonium oder Glucammonium steht. Ihre Herstellung erfolgt beispielsweise durch Schotten-Baumann Acylierung von Glutaminsäure mit Fettsäuren, Fettsäureestern oder -Chloriden. Verkaufsprodukte sind beispielsweise von der Hoechst AG, Frankfurt/DE oder der Ajinomoto Co. Inc., Tokyo/JP erhältlich. Eine Übersicht zu Herstellung und Eigenschaften der Acylglutamate findet sich von M.Takehara et al. in J. Am. Oil. Chem. Soc, 49, 143 (1972). Mischungen von Alkylglucosiden und Acylglutamaten werden in der Japanischen Patentanmeldung JP-A Hl/178 597 (Shiseido) beschrieben.
Figure imgf000010_0002
in which R 10 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and Z represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammomum, alkanolammonium or glucammonium. They are produced, for example, by Schotten-Baumann acylation of glutamic acid with fatty acids, fatty acid esters or chlorides. Sales products are available, for example, from Hoechst AG, Frankfurt / DE or Ajinomoto Co. Inc., Tokyo / JP. An overview of the production and properties of the acylglutamates can be found by M.Takehara et al. in J. Am. Oil. Chem. Soc, 49, 143 (1972). Mixtures of alkyl glucosides and acyl glutamates are described in Japanese patent application JP-A Hl / 178 597 (Shiseido).
Glutaminsäure stellt formal eines der Produkte dar, das man bei einer Totalhydrolyse von Proteinen erhalten würde. Tatsächlich führt die Hydrolyse von Proteinen jedoch zu Gemischen von Oligopeptiden, die noch im Mittel 5 bis 20 Aminosäureeinheiten aufweisen. Demzufolge stellen übliche Proteinfettsäurekondensate Acylierungsprodukte von Oligopeptiden dar. Acylglutamate unterscheiden sich von diesen Stoffen dadurch, daß sie gewissermaßen "Monomere" darstellen. Formally, glutamic acid is one of the products that would be obtained by total hydrolysis of proteins. In fact, however, the hydrolysis of proteins leads to mixtures of oligopeptides which still have an average of 5 to 20 amino acid units. As a result, conventional protein fatty acid condensates represent acylation products of oligopeptides. Acylglutamates differ from these substances in that they represent "monomers" to a certain extent.
Typische Beispiele für geeignete Acylglutamate, die im Sinne der Erfindung in Betracht kommen, sind Aniontenside, die sich von Fettsäuren mit 6 bis 22, vorzugsweise 12 bis 18 Kohlen-stoffatomen ableiten, wie beispielsweise C12/14- bzw. C12/18-Kokosfettsäure, Laurinsäure, Myristinsäure, Palmitinsäure und/oder Stearinsäure. Besonders bevorzugt sind Natrium-N- cocoyl- und Natrium-N-stearoyl-L-glutamat. Typical examples of suitable acylglutamates which are suitable for the purposes of the invention are anionic surfactants which are derived from fatty acids having 6 to 22, preferably 12 to 18 carbon atoms, such as C 12/14 - or C 12/18 - Coconut fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid. Sodium N-cocoyl and sodium N-stearoyl-L-glutamate are particularly preferred.
Proteinhydrolysate Protein hydrolyzates
Proteinhydrolysate stellen Abbauprodukte von tierischen oder pflanzlichen Proteinen, beispielsweise Collagen, Elastin oder Keratin und vorzugsweise Mandel- und Kartoffelprotein sowie insbesondere Weizen- und Sojaprotein dar, die durch saure, alkalische und/oder enzymatische Hydrolyse gespalten werden und danach ein durchschnittliches Molekulargewicht im Bereich von 600 bis 4000, vorzugsweise 2000 bis 3500 aufweisen. Obschon Proteinhydrolysate in Ermangelung eines hydrophoben Restes keine Tenside im klassischen Sinne darstellen, finden sie wegen ihrer dispergierenden Eigenschaften vielfach Verwendung zur Formulierung oberflächenaktiver Mittel. Übersichten zu Herstellung und Verwendung von Proteinhydrolysaten sind beispielsweise von G.Schuster und A.Domsch in Seifen Öle Fette Wachse, 108, 177 (1982) bzw. Cosm.Toil. 99, 63 (1984), von H.W.Steisslinger in Parf. Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein and in particular wheat and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in the range of 600 have up to 4000, preferably 2000 to 3500. Although protein hydrolyzates do not represent a surfactant in the classic sense due to the lack of a hydrophobic residue, they are widely used for the formulation of surface-active agents because of their dispersing properties. Overviews of the manufacture and use of Protein hydrolyzates are, for example, from G. Schuster and A. Domsch in Seifen Öle Fette Wachsen, 108, 177 (1982) and Cosm.Toil, respectively. 99, 63 (1984), by HW Steisslinger in Parf.
Kosm. 72, 556 (1991) und F.Aurich et al. in Tens. Surf. Det. 29, 389 (1992) erschienen. Aus der Deutschen Patentanmeldung DE-A1 40 09 616 (Henkel) sind ferner flüssige Körperreinigungsmittel bekannt, die neben Alkylglucosiden und Proteinhydrolysaten noch in untergeordneten Mengen Betaine enthalten können. Cosm. 72, 556 (1991) and F. Aurich et al. in tens. Surf. Det. 29, 389 (1992). From the German patent application DE-A1 40 09 616 (Henkel), liquid personal cleansing agents are also known which, in addition to alkyl glucosides and protein hydrolyzates, can also contain betaines in minor amounts.
Tensidgemische Mixtures of surfactants
Die Herstellung der erfindungsgemäßen Mischungen erfolgt beispielsweise durch Vermischen der einzelnen Tenside unter Erwärmen. In einer bevorzugten Ausführungsform der Erfindung werden jedoch niedrigviskose binäre Vorgemische hergestellt, beispielsweise aus 25 bis 75 Gew.-% der einzusetzenden Menge der Komponente a) und 100 % der Menge der Komponente c) einerseits und andererseits aus der verbliebenen Menge der Komponente a) und 100 Gew.-% der Komponente b); die Komponenten a) und b) sind in diesem Beispiel austauschbar. The mixtures according to the invention are prepared, for example, by mixing the individual surfactants with heating. In a preferred embodiment of the invention, however, low-viscosity binary premixes are produced, for example from 25 to 75% by weight of the amount of component a) to be used and 100% of the amount of component c) on the one hand and on the other hand from the remaining amount of component a) and 100% by weight of component b); Components a) and b) are interchangeable in this example.
Die erfindungsgemäßen Tensidgemische enthalten die Komponenten a), b) und c) vorzugsweise in den Gewichtsverhältnissen (30 bis 50) : (15 bis 35) : (15 bis 35). Unter verdünnten Mitteln sind solche zu verstehen, die einen Aktivsubstanzgehalt (nichtwäßrigen Gehalt) im Bereich von 5 bis 20 und insbesondere 10 bis 15 Gew.-% aufweisen. The surfactant mixtures according to the invention preferably contain components a), b) and c) in the weight ratios (30 to 50): (15 to 35): (15 to 35). Diluted agents are to be understood as meaning those which have an active substance content (non-aqueous content) in the range from 5 to 20 and in particular 10 to 15% by weight.
Gewerbliche Anwendbarkeit Industrial applicability
Die erfindungsgemäßen Tensidgemische zeichnen sich trotz des hohen Wasseranteils durch eine ausreichend hohe Viskosität im Bereich von 1.000 bis 50.000 mPas (Schergeschwindigkeit 1/ s) sowie vorteilhafte oszillierende Eigenschaften aus. Sie eignen sich beispielsweise zur Reinigung harter Oberflächen und insbesondere als Körper- und Haarreinigungs- und -Pflegemittel, wie beispielsweise Haarshampoos, Haarlotionen oder Schaumbäder, und können in diesem Zusammenhang als typische Inhaltsstoffe, Emulgatoren, Über fettungsmittel, Verdickungsmittel, Kationpolymere, Siliconverbindungen, biogene Wirkstoffe, Filmbildner, Konservierungsmittel, Färb- und Duftstoffe enthalten. Despite the high water content, the surfactant mixtures according to the invention are distinguished by a sufficiently high viscosity in the range from 1,000 to 50,000 mPas (shear rate 1 / s) and advantageous oscillating properties. They are suitable, for example, for cleaning hard surfaces and in particular as body and hair cleaning and care products, such as, for example, hair shampoos, hair lotions or bubble baths, and can be used in this connection as typical ingredients, emulsifiers, and over contain greasing agents, thickening agents, cation polymers, silicone compounds, biogenic agents, film formers, preservatives, colorants and fragrances.
Als Emulgatoren kommen sowohl bekannte W/O- als auch O/W- Emulgatoren wie beispielsweise gehärtetes und ethoxyliertes Ricinusöl, Polyglycerinfettsäureester oder Polyglycerinpolyricinoleate bzw. Polyglycerinpoly-12-hydroxystearate in Frage. Suitable emulsifiers are both known W / O and O / W emulsifiers such as, for example, hardened and ethoxylated castor oil, polyglycerol fatty acid esters or polyglycerol polyricinoleates or polyglycerol poly-12-hydroxystearates.
Als Überfettungsmittel können Substanzen wie beispielsweise polyethoxylierte Lanolinderivate, Lecithinderivate, Polyolfettsäureester, Monoglyceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen.  Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
Geeignete Verdickungsmittel sind beispielsweise Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon, Tenside wie beispielsweise Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkyloligoglucoside sowie Elektrolyte wie Kochsalz und Ammoniumchlorid. Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as, for example, fatty alcohol distribution with fatty alcohols such as fatty alcohol or alkyl oligoglucosides and electrolytes such as table salt and ammonium chloride.
Geeignete kationische Polymere sind beispielsweise kationischen Cellulosederivate, kationischen Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vmylpyrrolidon/Vinylimidazol-Polymere wie z.B. Luviquat® (BASF AG, Ludwigshafen/ FRG), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide wie beispielsweise Lauryldimonium hydroxypropyl hydrolyzed Collagen (Lamequat®L, Grünau GmbH), Polyethylenimin, kationische Siliconpolymere wie z.B. Amidomethicone oder Dow Corning, Dow Corning Co./US, Copolymere der Adipinsäure und Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine®, Sandoz/CH), Polyaminopolyamide wie z.B. beschrieben in der FR-A 22 52 840 sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniertes Chitosan, gegebenenfalls mikrokristallin verteilt, kationischer Guar-Gum wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Celanese/US, quaternierte Ammoniumsalz-Polymere wie z.B. Mirapol® A15, Mirapol® AD-1, Mirapol® AZ-1 der Miranol/US. Geeignete Siliconverbindungen sind beispielsweise Dimethylpolysiloxane, Methyl- phenylpolysiloxane, cyclische Silicone sowie amino-, fettsäure-, alkohol-, polyether-, epoxy¬, fluor- und/oder alkylmodifizierte Siliconverbindungen. Suitable cationic polymers are, for example, cationic cellulose derivatives, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized Vmylpyrrolidon / vinylimidazole polymers such as, for example, Luviquat® (BASF AG, Ludwigshafen / FRG), condensation products of polyglycols and amines, such as, for example, collagen hydrolyzylated collagen polypolyphenolated collagen polypropylene (Lamequat®L, Grünau GmbH), polyethyleneimine, cationic silicone polymers such as Amidomethicone or Dow Corning, Dow Corning Co./US, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetrimamine (Cartaretine®, Sandoz / CH), polyaminopolyamides as described, for example, in FR-A 22 52 840 and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, cationic guar gum such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese / US, quaternized ammonium salt polymers such as M irapol® A15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol / US. Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine and / or alkyl modified silicone compounds.
Unter biogenen Wirkstoffen sind beispielsweise Pflanzenextrakte und Vitaminkomplexe zu verstehen. Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.
Gebräuchliche Filmbildner sind beispielsweise Chitosan, mikrokristallines Chitosan, quaterniertes Chitosan, Polyvinylpyrrolidon, VinylpyπOlidon-Vinylacetat-Copolymerisate, Polymere der Acrylsäurereihe, quaternäre Cellulose-Derivate, Kollagen, Hyaluronsäure bzw. deren Salze und ähnliche Verbindungen. Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyπOlidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure. Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
Als Perlglanzmittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremonoglycolester in Betracht. Suitable pearlizing agents are, for example, glycol distearic acid esters such as ethylene glycol distearate, but also fatty acid monoglycol esters.
Als Farbstoffe können die für kosmetische Zwecke geeigneten und zugelassenen Substanzen verwendet werden, wie sie beispielsweise in der Publikation "Kosmetische Färbemittel" der Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, S.81-106 zusammengestellt sind. Diese Farbstoffe werden üblicherweise in Konzentrationen von 0,001 bis 0,1 Gew.-%, bezogen auf die gesamte Mischung, eingesetzt. The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
Der Gesamtanteil der Hilfs- und Zusatzstoffe kann 1 bis 50, vorzugsweise 5 bis 40 Gew.-% - bezogen auf die Mittel - betragen. The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. Beispiele The following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples
Zur Bestimmung des viskoelastischen Verhaltens wurden wäßrige Tensidmischungen mit einem Aktivsubstanzgehalt von 12 Gew.-%, gegenbenenfalls unter Zusatz von 1 bis 3 Gew.-% Kochsalz - bezogen auf den Feststoffgehalt der Mischungen - bei 20°C in einem Rheometrics RFSII-Rotationsrheometer untersucht. Bestimmt wurde die Vikosität bei einer Schergeschwindigkeit von 1 bzw. 30 s/m sowie in Oszillationsexperimenten der Elastizitätsmodul G' und der Viskositätsmodul G". Zur Herstellung der Mischungen wurden zunächst niedrigviskose binäre Vorgemische aus 50 Gew.-% der Komponente a) und 100 Gew.-% der Komponente b) einerseits und 50 Gew.-% der Komponente a) und 100 % des Cotensids c) bereitet und unter Rühren vermischt. Die Zusammensetzung der Rezepturen 1 bis 13 sind in Tabelle 1, die Ergebnisse der Viskositätsmessungen in Tabelle 2 zusammengefaßt. To determine the viscoelastic behavior, aqueous surfactant mixtures with an active substance content of 12% by weight, optionally with the addition of 1 to 3% by weight of sodium chloride, based on the solids content of the mixtures, were investigated at 20 ° C. in a Rheometrics RFSII rotary rheometer. The viscosity was determined at a shear rate of 1 or 30 s / m and in oscillation experiments, the modulus of elasticity G 'and the viscosity modulus G ". To prepare the mixtures, low-viscosity binary premixes of 50% by weight of component a) and 100% by weight were first used % of component b) on the one hand and 50% by weight of component a) and 100% of cosurfactant c) and mixed with stirring The composition of recipes 1 to 13 are in Table 1, the results of the viscosity measurements in Table 2 summarized.
Figure imgf000015_0001
Figure imgf000015_0001
Legende: APG = Kokosalkyloligoglucosid (Plantaren® APG 1200)  Legend: APG = coconut alkyl oligoglucoside (Plantaren® APG 1200)
BET = Kokosfettsäureamidobetain (Dehyton® K)  BET = coconut fatty acid amido betaine (Dehyton® K)
FAES = Fettalkoholethersulfat (Texapon® NSO)  FAES = fatty alcohol ether sulfate (Texapon® NSO)
ACG = Acylglutamat (Hostapon® KCG)  ACG = acylglutamate (Hostapon® KCG)
WPHY = Weizenproteinhydrolysat (Gluadin® WK)  WPHY = wheat protein hydrolyzate (Gluadin® WK)
CMGS = Kokosmonoglyceridsulfat-Natriumsalz
Figure imgf000016_0001
CMGS = coconut monoglyceride sulfate sodium salt
Figure imgf000016_0001

Claims

Patentansprüche claims
1. Verdünnte Tensidgemische mit erhöhter Vikosität, enthaltend bezogen auf Tensidanteil a) 30 bis 70 Gew.-% Alkyl- und/oder Alkenyloligoglykoside, 1. Diluted surfactant mixtures with increased viscosity, containing 30 to 70% by weight of alkyl and / or alkenyl oligoglycosides, based on surfactant content a),
b) 15 bis 50 Gew.-% Betaintenside und  b) 15 to 50% by weight betaine surfactants and
c) 15 bis 50 Gew.-% Co-Tenside ausgewählt aus der Gruppe, die gebildet wird von Fettalkoholethersulfaten, Monoglycerid(ether)sulfaten, Acylglutamaten und Proteinhydrolysaten, mit der Maßgabe, daß sich die Mengenangaben zu 100 Gew.-% Aktivsubstanz ergänzen.  c) 15 to 50% by weight of co-surfactants selected from the group consisting of fatty alcohol ether sulfates, monoglyceride (ether) sulfates, acylglutamates and protein hydrolyzates, with the proviso that the amounts add up to 100% by weight of active substance.
2. Tensidgemische nach Anspruch 1, dadurch gekennzeichnet, daß sie Alkyl- und Alkenyloligoglykoside der Formel (I) enthalten, 2. surfactant mixtures according to claim 1, characterized in that they contain alkyl and alkenyl oligoglycosides of the formula (I),
R1O-[G]p (I) in der R1 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 KohlenstofFatomen, G für einen Zuckerrest mit 5 oder 6 KohlenstofFatomen und p für Zahlen von 1 bis 10 steht. R 1 O- [G] p (I) in which R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.
3. Tensidgemische nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß sie Betaine der Formel (II) enthalten, 3. surfactant mixtures according to claims 1 and 2, characterized in that they contain betaines of formula (II),
z
Figure imgf000017_0001
in der R2 für Alkyl- und/oder Alkenylreste mit 6 bis 22 KohlenstofFatomen, R3 für Wasserstoff oder Alkylreste mit 1 bis 4 KohlenstofFatomen, R4 für Alkylreste mit 1 bis 4 KohlenstofFatomen, n für Zahlen von 1 bis 6 und X für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. e.g.
Figure imgf000017_0001
in which R 2 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 3 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 4 for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X for a Alkali and / or alkaline earth metal or ammonium.
4. Tensidgemische nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß sie Be-taine der Formel (III) enthalten, 4. surfactant mixtures according to claims 1 to 3, characterized in that they contain betaines of the formula (III),
Figure imgf000018_0001
in der R5CO für einen aliphatischen Acylrest mit 6 bis 22 KohlenstofFatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R3, R4, n und X die oben angegebenen Bedeutungen haben.
Figure imgf000018_0001
in which R 5 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R 3 , R 4 , n and X have the meanings given above.
5. Tensidgemische nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß sie Fettalkoholethersulfate der Formel (IV) enthalten, 5. surfactant mixtures according to claims 1 to 4, characterized in that they contain fatty alcohol ether sulfates of the formula (IV),
R8O-(CH2CH2O)mSO3Z (TV) in der R8 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, n für Zahlen von 1 bis 10 und Z für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. R 8 O- (CH 2 CH 2 O) m SO 3 Z (TV) in R 8 for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n for numbers from 1 to 10 and Z for a Alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
6. Tensidgemische nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie Mo- noglycerid(ether)sulfate der Formel (V) enthalten, 6. surfactant mixtures according to claims 1 to 5, characterized in that they contain monoglyceride (ether) sulfates of the formula (V),
Figure imgf000018_0002
in der R9CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30 und Z für ein Alkalioder Erdalkalimetall steht.
Figure imgf000018_0002
in which R 9 CO stands for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30 and Z for an alkali or alkaline earth metal.
7. Tensidgemische nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß sie Acylglutamate der Formel (VI) enthalten, 7. surfactant mixtures according to claims 1 to 6, characterized in that they contain acylglutamates of the formula (VI),
Figure imgf000019_0001
in der R10CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 und/ oder 1, 2 oder 3 Doppelbindungen und Z für Wasserstoff, ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glu-cammonium steht.
Figure imgf000019_0001
in which R 10 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and Z represents hydrogen, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium .
8. Tensidgemische nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß sie Weizenproteinhydrolysate enthalten. 8. surfactant mixtures according to claims 1 to 7, characterized in that they contain wheat protein hydrolyzates.
9. Tensidgemische nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, daß sie die Komponenten a), b) und c) in den Gewichtsverhältnissen (30 bis 50) : (15 bis 35) : (15 bis 35) enthalten. 9. surfactant mixtures according to claims 1 to 8, characterized in that they contain the components a), b) and c) in the weight ratios (30 to 50): (15 to 35): (15 to 35).
10. Tensidgemische nach den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß sie einen Aktivsubstanzgehalt im Bereich von 5 bis 20 Gew.-% aufweisen. 10. surfactant mixtures according to claims 1 to 9, characterized in that they have an active substance content in the range of 5 to 20 wt .-%.
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WO1999027062A1 (en) * 1997-11-26 1999-06-03 Henkel Kommanditgesellschaft Auf Aktien Dish washing detergent with a specific viscosity profile
FR2826017A1 (en) * 2001-06-15 2002-12-20 Cognis France Sa Surfactant mixtures useful in cosmetics, body care products, shower gels or shower baths and baby care products comprises oligoglycosides, betaines and alkyl ether sulfates
WO2011008281A1 (en) 2009-07-14 2011-01-20 Rhodia Operations Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions
WO2011034444A1 (en) * 2009-09-17 2011-03-24 Polygon (Nz) Limited Herbicidal surfactant formulations

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DE19805671C2 (en) * 1998-02-12 1999-12-16 Henkel Kgaa Process for the preparation of haze-free detergent mixtures

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WO1999027062A1 (en) * 1997-11-26 1999-06-03 Henkel Kommanditgesellschaft Auf Aktien Dish washing detergent with a specific viscosity profile
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WO2011034444A1 (en) * 2009-09-17 2011-03-24 Polygon (Nz) Limited Herbicidal surfactant formulations
AU2010296099B2 (en) * 2009-09-17 2014-09-18 Kin-Wai Mok Herbicidal surfactant formulations

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